Condensation products and methods of preparing and using same



Patented Aug. 7, 1 945 CONDENSATION PRODUCTS AND METHODS OF PREPARING AND USING'SAME Eugene Lieber, West New Brighton, Staten Island,

and Marvin E. ThornenBrooklyn, N.

Y., as-

signors to Standard Oil Development Company,

a corporation of Delaware No Drawing. Application November 18, 1941 Serial N0. 419,602

3 Claims. ((1252-52) This invention relates to a novel type of con- .densation products and to methods of preparing such products and using them for various purposes, more particularly as pour depressors in waxy lubricating oils.

Broadly, the invention comprises the production of condensation products which have wax-modifying properties by condensing a low molecular weight aliphatic oxide with an aromatic compound. This condensation is preferably carried out by the use of Friedel-Crafts catalysts according to procedures commonly used for effecting such condensations.

The aliphatic oxides to be used are preferably lower alkylene oxides having a total of less than carbon atoms. Such alkylene oxides may be considered as chemical compounds having the general formula R-CH-CH-R' in which R and R are either alkyl hydrocarbons or hydrogen and they may be similar or dissimilar. The R and' R together preferably have less than 6 carbon atoms. Some specific examples of suitable aliphatic oxides coming within the scope of the above description are the following: amylene oxide,- butylene oxide, propylene oxide, ethylene oxide, and evensome slightly higher in molecular weight.

The aromatic compounds to be used as the other primary starting material for the chemical condensation of this invention are preferably hythol, alpha or beta naphthylamine, anthracene,

phenanthrene, picene, or compounds containing two or more different substituents, such as amino toluene or hydroxy toluene, etc. The aromatic compounds to be used should contain one or more replaceable hydrogen atoms on the aromatic nucleus and it is preferable that the aromatic nucleus should not have more than two substituents already attached thereto.

The proportions in which the lower alkylene 2-4 mols, of alkylene oxide per mol of aromatic compound.

Although it is possible to carry-out this chemical condensation without the use of any inert solvent or diluent, it is preferable that such a liquid medium be used, such as a heavy naphtha or kerosene which may, if desired, be pretreated with sulfuric acid or aluminum chloride or some other suitable material to make itinert, or suitable chlorinated hydrocarbon compounds, e. g., tetrachlorethane, which are inert under the reaction conditions used for carrying out this condensation. If a solvent or diluent is used the amount thereof should be about V2 to 10 volumes, preferably-about 1-5 volumes, per volume of mixed reactants.

To effect the condensation it is preferable to use a Friedel-Crafts catalyst, preferably anhydrous aluminum chloride, although other Friedel- Crafts catalysts can be used, such as boron fluoride, zinc chloride, ferric chloride, titanium tetrachloride and boron trichloride. The amount of catalyst to be used will, of course, depend to some extent upon the relative reactivity of the particular reactants, as well as the amount of 501- parting from the .scope of the invention. For' instance, the order of adding the reactants and catalysts may be varied, as, for example, adding the catalyst last or adding the alkylene oxide last.

The reaction conditions of temperature andtime will, of course, depend upon the reactivity of the reactants and upon the relative amount of catalyst and solvent but usually a temperature ranging from about room temperature up to about 300 F., but preferably not above 250 F., may be employed, the reaction time depending upon the other variables being usually between about /2 oxides and the aromatic compounds should be mixed for carrying out the chemical condensation of this invention may vary over a substantially wide range, such as about 05-10 mols, preferably hour and 10 hours, with about 1-4 hours being the usual time required. 7

After the condensation has beencompleted, the reaction mixture is preferably cooled and diluted with a suitable volatile, inert solvent, preferably the same as the diluent used during the reaction if one was used, and then the catalyst is hydrolyzed or neutralized by any of the methods com- -monly used in Friedel-Crafts reactions, as, forinstance, treating the reaction mixture with water, a dilute aqueous solution of caustic soda, alcohol, or a mixture of water and alcohol. The mixture is then settled or otherwise separated into a solvent layer and an aqueous or sludge layer, which latter is removed. The solvent or extract layer is then subjected to distillation with fire and steam or with vacuum, e. g., about 5-50 mm. mercury absolute pressure, up to a final temscribed in detail in narrative form and then all of the experimental data are summarized in a table indicating the kinds and proportions of materials used, as well as reaction conditions and perature of about 500 F. or 600 F., in order to 5 the nature of the resulting product, so that the remove the solvent and low-boilingproducts and diflerences between various examples can be to leave the desired high molecular weight conreadily observed. densation product as distillation residue. t a 3-1it -4 k round b tt flask fit. This condensation product, which is generally ted with a mechanical stirrer, reflux condenser, resinous in nature but may occasionally be in 10 thermometer and dropping funnel were placed 58 the form of a viscous oil and has a color ranggrams of propylene oxide having the chemical ing from a reddish-green to a brown or black formula and may be viscous, stringy, or brittle, is soluble C r-H a in mineral oils and has the property of modifying the crystal structure of wax, such as'parafl fin wax, when added to compositions contain- 128 grams of naphthalene and 500 cc. of kerosene ing the Same- For tanc en about (heavily treated with sulfuric acid before use) preferably 0.2-5%, of this wax modifier is added as solvent. Means were provided for cooling and a to a y u cating oil, such as a Pennsylvan a heating the reaction flask. The mechanical stir-' other Daraffimo ype o lubricating oil having rer was started and while maintaining a tema relatively high pour point, the resultant blend perature of 80 F., 135 grams of anhydrous A1013 will have a substantially lower pour point. In were slowly added to the reaction mixture. After other words, this wax modifier is an effective the addition of the A101: the reaction mixture pour depressor for waxy oils. was heated to 150 F., and maintained thereat Alth h th ex ct me hani m of the ope for 4 hours, after which time it was diluted with tion of this invention and the exact nature of the a further quantity of kerosene, cooled to 100 F., chemical structure of the resulting products are and the AlCla destroyed by slowly adding 500 cc. not well understood, it is believed the lower alkylof amixture of isopropyl alcohol and water. ene oxide condenses with the aromatic compound After settling a d removal of t catalyst-sludge, in e y as to have an interlinking effect so the kerosene extract was washed free of acid and s t ld up p du ts of a w or th dimene then distilled with fire and stea to 600 R. in Sional Chain y Structure, and also to s order to remove solvent and low-boiling products. extent having yl ps ttac ed as Si e A bottoms residue comprising 121 grams of a chains'to one or more of the aromatic nuclei in brown, stringy resin was obtained as product. the high mo e r We t ain type produc In other examples the proportions of propylene Its molecular weight appears to be in therange oxide and naphthalene were varied, some other of about 500-1500. aromatic compounds were used, various amounts A small amount of this wax modifier is also of aluminum chloride were used and in some useful as a dewaxing aid for removing wax from cases tetrachlorethane was used instead of keromineral lubricating oils of undesirably high wax sene as solvent, and finally in a number of cases content, and in similarly small amounts this wax the propylene oxide was added last instead of modifier may also be incorporated into parafiin adding the aluminum chloride last In all the wax or compositions containing the same to be tests the same temperature and time of reaction used for various purposes, such as for coating or were used.

Table I Aromatic compound Solvent P Test Propylene lCls, Yield, 33; Color No oxide, 8. Name GT Egg. g e t figig- F 1 1 135 121 0 Br.stringyresin.

2 2 135 78 0 Dark resin. 3 200 105 5 Brown resin. 4 200 116 5 Black brittle resin. 5 A0 200 78 --10 Do. 6. Amyl naphthalene. 1 3' 3 Do. 7 90 Naphthalene 2 82 Do 8-.." 87 Anthracene 198 102 5 Black resin. 9 87 198 100 5 Red-gr.visc-stringy oil. 10 87 200 117 -10 Brown resin. 11A 87 Fluo'rene 200 104, 0 Do.

1 A S. T. M. pour point of 2% blend in waxy lube oil having pour point of +30 1 Added last.

kerosene, fuel oil, Diesel fuel, etc. For the sake of illustration but without intending to limit the invention to the particular materials used or to the particular reaction conditions used, some experimental'data are given down to temperatures from 0 F. to .-25 R, or

lower.

It is not intendedv that this invention be limited to any of the specific examples which were given merely for the sake of illustration, nor unnecessarily to any theoryof the mechanism of the operation of the invention but only by the apherewith. Only the first example will be de pended claims in which it is intended to claim all novelty inherent in the invention as well as equivalents coming within the scope and spirit of the invention.

We claim;

1. A composition comprising a major proportion of a mineral lubricating oil and a small amount of a Friedel-Crafts condensation prodnot of an alkylene oxide having less than 10 carbon atoms with an aromatic compound adapted to Friedel-Crafts condensation through replacea-ble hydrogen atoms on the aromaticnucleus selected from the group consisting of aromatic hydrocarbons and alkyl, hydroxy and amino derivatives thereof, said condensation product being substantially non-volatile at temperatures up to about 600 F. under fire and steam distillation and having pour depressing properties.

2. A composition comprising a major proportion of a waxy mineral lubricating oil and a small but pour depressing amount of a high solved therein a pour-depressing amount between the approximate limits of 0.5 and 5.0% of a high molecular weight Friedel-Craits condensation product of an alkaline oxide having 2 to '7 carbon atoms with a polynuclear aromatic hydrocarbon adapted to Frledel-Crafts condensation through replaceable hydrogen atoms on the aromatic nucleus, said condensation product being substantially non-volatile up to about 500 F. under fire and steam distillation.

EUGENE LIE-BER. MARVIN E. THORNER. 

